Fe（2＋）活化CH_3X（X=H,Cl）中C—H,C—Cl键的理论研究

• 作 者: 孙小丽 李吉来 黄旭日 孙家锺
• 机 构: 吉林大学理论化学研究所理论化学国家重点实验室,
• 出 处: 化学学报
• 发表日期: 2012年11期
• 关键词: SN2 insertion abstraction reaction mechanism activation barrier electronic struc

采用密度泛函理论(DFT)详尽地研究了Fe2+与CH3X(X=H,Cl)的反应机理.结果表明在所有通道中,反应4的H提取能垒最低(Ga=0.23 kcal/mol),氧化插入机制和SN2取代机制没有竞争性.详尽的电子结构分析表明由于金属3d与底物的σ*C—X可以最好的重叠,从而Fe2+从前端进攻C—X键有利于反应.该研究揭示了其微观本质,为Fe2+活化C—X键等相关研究提供理论线索和依据.

The reaction mechanism between Fe2 + and CH3X (X = H, Cl) has been studied in detail by using density functional theory (DFT). The results show that the energy barrier of reaction H is the lowest (Ga = 0.23 kcal / mol) The oxidative insertion mechanism is not competitive with the SN2 substitution mechanism, and exhaustive analysis of the electron structure suggests that Fe2 + favors the reaction by attacking the C-X bond from the front due to the best overlap between the metal 3d and the substrate σ * C-X Reveal its microscopic nature, provide theoretical clues and basis for the relevant research Fe2 + activated C-X bond.